Novel nanostructured hybrid electrospun polyacrylonitrile (PAN) yarns with different graphene ratios were prepared using liquid crystal graphene oxide (LCGO) and PAN. It was found that the well-dispersed LCGO were oriented along the fiber axis in an electrified thin liquid jet during electrospinning. The graphene oxide sheets were well dispersed in the polar organic solvent, forming nematic liquid crystals upon increasing concentration. Twisted nanofibers were produced from aligned nanofibrous mats prepared by conventional electrospinning. It was found that the mechanical properties of the twisted nanofiber yarns increased even at very low LCGO loading. This research offers a new approach for the fabrication of continuous, strong, and uniform twisted nanofibers which could show promise in developing a novel carbon fiber precursor.